Cationic heterocyclic disazo dyes



United States Patent Office 3,415,809

Patented Dec. 10, 1968 Y represents an anionic material, eg. CH SO or 3,415,809 CATIONIC HETEROCYCLIC DISAZO DYES (ERG-Se a John G. Fisher and Clarence A. Coates, Jr., Kingsport,

Tenn., assignors to Eastman Kodak Company, Roch- 5 and the1ike ester, a a corporation of New Jersey The heterocyclic azo dyes of the invention are prepared N0 Drawmg' g g gg k L427 by two principal methods. The choice of method is dependent on whether the desired dye is to be symmetrical or unsymmetrical.

ABSTRACT OF THE DISCLOSURE It is desired that the dye be symmetrical in structure, a bis urea or a bis urethane coupling component having Azo compounds containlng two th1azoly-, benzoth1athe formula zo1yl-, thiadiazolyl-, triazolyl-, or benzimidazolyl-azo- R R, aniline groups, the two aniline nitrogen atoms being joined by a group having the formula 0 'R'2N (I 0 wherein all symbols are defined above and wherein the ll lt prime symbols are the same as the principal symbols, is

coupled with two equivalents of the diazonium salt of a in which 3 and 's each is alkylene, X is or heterocyclic compound having the formula --NH-, and Z is alkylene, phenylene, bis(phenylene) methylene, bis(methylene)phenylene, biphenylene or naphthylene, are useful as dyes for polyacrylonitrile textile 1 (I materials. wherein A is defined above. Thus, the product of the coupling reaction of a compound of Formula II with a compound of Formula III has the nonquaternized struc- This invention relates to novel heterocyclic azo comture of Formula I wherein the principal and prime symbols pounds and, particularly, to novel cationic heterocyclic represent the same structures. The coupling reaction is azo dyes for synthetic fibers, yarns and fabrics. conventional and will be more fully described in the ex- The novel cationic heterocyclic azo compounds of the amples set forth hereinafter. Upon obtaining a compound invention are characterized by the general formula having the structure of Formula I in the nonquaternized wherein form, the compound is quaternized with an alkylating A and A represent the same or difierent radical or group agent to provide the symmetrical cationic heterocyclic azo of atoms necessary to complete the heterocyclic ring, dyes of the invention. Thus, the reaction sequence is illuswhich ring may be a thiazole ring, a benzothiazole ring, trated as follows:

a 1,3,4-thiadiazole ring or a benzimidazole ring and The bis coupling components of Formula II are prethe like; pared by reacting tWo moles of an N-hydroxyalkyl aniline R represents alower alkyl radical, e.g. methyl; or a benzyl or diphenyl amine or an N-aminoalkylaniline or diphenradical; ylamine having the formula B and B represent the same or different monocyclic car- R2 bocyclic aromatic radicals of the benzene series, e.g. phenylene and substituted phenylene such as o,m- B N R3X (IV) tolylene and h lik wherem the symbols are defined above, with a diisocyanate R and Rg represent the same or different alkyl radicals, having the formula e.g., methyl, ethyl and the like, or the same or diiferent (V) monocyclic carbocyclic aromatic radicals, e.g. phenyl or substituted phenyl such as tolyl; wherein Z is defined above. When X is oxygen, the his R and R' represent a straightor branched-chain lower coupling component will be a urethane and when X is alkylene radical, e.g. methylene, ethylene and the like; -NH, the his coupling component will be a urea. X and X represent O-- or NH- and may be the If it is desired that the dye be unsymmetrical in strucsame or different; ture, a different method than that described above is used.

Z represents alkylene, e.g. hexamethylene; arylene, e.g. To prepare the unsymmetrical heterocycli-c azo dye, the phenylene, p-phe'nylene, p-xylylene; alkarylene, e.g. diazonium salt of a heterocyclic compound having the methylenebis (phenylene); aralkylene, e.g. tolylene, structure of Formula III is coupled with a compound xylylene or naththylene and the like; and having free hydroxyl or amino groups of Formula IV.

The monoheterocyclic dye thus prepared has the formula:

N R, A C-N=NB N-R:X (v I) wherein the symbols are defined above. By subsequently reacting the dye of Formula V1 with a diisocyanate of Formula V, a product is obtained which has the formula 4 97-98 C. Analysis for C and H indicated the compound of the following structure:

I ll -NC in. o o NI-I o In N R2 A /\(3 N:N B I|\J R3XCON Z NCO (VII) Of the couplers of Formula used in the following examples were prepared in the manner described above E g g 9 t; gg g i g i x using the appropriate diisocyanate of Formula V with n ye avmg e r u a a y g two equivalents of the hydroxy or amino compound of s we ure Formula VI.

N R R N l l 2 Preparation of symmetrical dyes ACN=NB-NRaXOCN-ZNCOXR3NB-N=N-CA EXAMPLE 1 is obtained wherein the heterocyclic end groups have nonidentical structures. Upon alkylation, a compound of An amount of 1.5 g. of Z-ammobenzothiazole was dis- Formula I is obtained. The reaction sequence is as folsolved in 58 g. of H cooled to 0 C. and treated lows: with a solution of nitrosyl sulfuric acid prepared from N\ R: /N\ Ill: A CN=N BI I-R X A:CN=NBNR3X OGN-Z-NCO (III) (IV) (v1) (V) N R: N R:

(VII) The following examples will serve to illustrate the preparation of the couplers and formation of the dyes of the invention therefrom.

Preparation of the couplers.-Bis urea coupler (coupler No. 1)

A solution of 35.6 g. N-ethyl-N-fl-aminoethyl-m-toluidine in 80 ml. of benzene was added slowly to 17.4 g. of tolylene-2,4-diisocyanate in 20 ml. of benzene. After the addition was complete and the exothermic reaction had subsided, the solution was heated at reflux for three hours. It was then poured into 125 ml. of ethanol and allowed to stand. The crystalline product was filtered off, washed with ethanol and dried at room temperature to give 51 g. of white product melting at 155 C. after recrystallization from ethanol. Analysis for C and H indicated the compound of the following structure:

.72 g. NaNO and 5 ml. of H SO (d. 1.84) at 0-5 C. The diazotization was completed by stirring at 3-6 C. for 2 hrs. This solution was added to an internally ice cooled solution of 2.51 g. of the bis urethane prepared from two equivalents of Np-hydroxyethyl-N-ethyl-m-toluidine and tolylene-2,4-diisocyanate dissolved in dilute sulfuric acid. After 2 hrs. coupling the mineral acid was destroyed by addition of ammonium acetate and the coupling mixture was diluted to 800 ml. by addition of water. The precipitated dye was collected on a funnel, washed with water and dried at room temperature.

EXAMPLE 2 An amount of 0.5 g. of the dye of Example 1 was heated with 10 ml. of dirnethyl sulfate at -95 C. for 1 hr. The blue solution was drowned in ether and the resulting solid collected on a funnel, washed with ether Bis urethane coupler (coupler N0. 2)

A mixture of 33 g. of N-ethyl-N-fi-hydroxyethylaniline, 17.4 g. tolylene-2,4-diisocyanate, and ml. benzene CzI-Is was stirred and refluxed for 3 hours. While still hot, the solution was poured into a 250 ml. beaker and allowed to stand overnight at room temperature. The bis-urethane precipitated and was filtered off, washed with benzene,

o 0 II i 17021140 CHN and dried in a vacuum desiccator. This dye imparts fast reddish-blue shades to Verel and Orion 42. This dye has the following structure:

(III-I CnHs EXAMPLE 3 An amount of 10 ml. of 1:5 acid (1 part propionic:5 parts acetic acid) was added to a solution of nitrosyl sulfuric acid prepared from .72 g. of NaNO and 5 ml.

and dried. The yield was 40.9 g. of a white solid, M.P. 0!? H 80 below 20 C. Then, 1.76 g. of 2-amino-4-phenylthiazole was added portionwise below 5 0, followed by a second ml. portion of 1:5 acid at the same temperature. After stirring for 2 hrs. at 3-5 C., the diazo solution was added to a solution of 2.65 g. of coupler No. 1 dissolved in ml. of 1:5 acid cooled in an ice bath. The coupling mixture was neutralized to brown on Congo Red paper with ammonium acetate and allowed to stand for 2 hrs. with occasional stirring. The dye was isolated by drowning in 600 ml. water, filtering and washing with water.

EXAMPLE 4 An amount of 1 g. of the product of Example 3 was dissolved in 150 ml. of chlorobenzene and treated washed with about '50 ml. of water, and dried at room temperature. It dyes Verel and Orlon 42 in violet shades I 0 i NCzHrO dHNCmQ-OHZNHG 0 CZHAN 6 EXAMPLE 5 An amount of 0.5 g. of an azo dye prepared from coupling 2-diazo-5-methylthio-1, 3, 4-tlhiadiazole to the reaction product of two equivalents of lN-fl-hydroxyethyldiphenylamine with p-xylylene diisocyante was heated With 10 g. of methyl-p-toluene sulfonate at 90-95 C. for 1.5 hr. The bluish solution was drowned in ether; the ether decanted from the precipitated quaternary dye and the latter dissolved in water by warming, filtered and allowed to cool. The dye was isolated by addition of ZnCl and NaCl, filtering and washing with 5% NaCl solution. It dyes Verel and Orlon 42 in reddish blue shades. This dye has the structure:

a N-N N=Nls l som EXAMPLE 6 'One gram of the zero dye prepared from the reaction of two equivalents of 2-diazo-1, 3, 4-triazole with the coupler prepared from the reaction of two equivalents of N-ethyl-N-[i-hydroxyethylaniline with methylenebisphenylenediisocynate was heated in 10 ml. of dimethylsulfate for 1% hr. The red solution was poured into water and warmed until the excess dimethylsulfate had decomposed, charcoal was added and the solution filtered. Addition of potassium iodide to the cooled filtrate and has the following structure:

CH; (3H

I -N=N N=N LS/ S CH3 CH3 21 CH3 l i I ITICflHriHNI'IN NHCNHCIHl I CnHs CzHs gave a dye which imparts red shades to acrylic fibers and has the formula 0 i l ionzno ('iHNQ-CHrQ-NH o 0 021m EXAMPLE 7 The dyes illustrated in the examples in Table :1, below, were prepared in the manner described in the preceding examples. The column headings corresond to the structure of formula 1, above. The table contains only the symetrical dyes. Thus, A=A, B=B, R R R =R Preparation of unsymmetrical dyes EXAMPLE 13 An amount of 1.44 g. of the dye prepared from 2- aminothiazole and N-fl-aminoethyl-N-ethyl-m-toluidine was dissolved in 50 ml. of dry dimethlformamide containing 0.87 g. of tolylene diisocyanate. After stirring for 0.5 hr. at room temperature the reaction mixture was heated at 90-95" C. for 3 hr. Then a solution of 1.70 g. of the dye prepared from 2-arninobenzothiazole 10 and N- 3-aminoethyl-N-ethyl-m-toluidine in 50 ml. of dry dimethylformamide was added. After heating and stirring for 72 hr., the red solution was drowned in water and the solid product was isolated and dried. It was heated in 20 ml. of dimethylsulfate at 95-100" C. for 1.5 hr., drowned in ether and the blue solid collected on 40 a funnel, washed with ether and dried in a vacuum desic- TABLE I Example A B R: R: X Z Color on Number Orlon 42 8 'C2 s C2H4 0 -CHa Blue.

9 C:Hs -01H4 NH Violet.

N/ CH3 I C 3 1o Q -ciH5 C2H4 NH Do u 11 N- -o,m CH:CH 0 CH3 Blue.

ll HG 12 -CIH5 CHz-GH 0 (CH2)5 DO.

9 cator. This dye imparts fast reddish-blue shades to Orlon and Verel. It has the structure:

llIzNlis/ Following the procedure of Example 13 and using identical quantities of reagents, the diisocyante was replaced by p-Xylylene diisocyanate. The dye obtained imparts fast reddish-blue shades to Orlon and Verel. It

TABLE IIC011tlnucd Example B B X X Z Shade on Number Orlon l CH3 CH3 w H O I CH CH2 r 11 --Q- NH l C 3 18 Q Q NH NH 1 CH3 CH3 w 19 43- Q NH The cationic heterocyclic azo dyes of the invention can be used for dyeing materials including synthetic polymer fibers, yarns and fabrics giving a variety of fast shades including blue, red, and violet when applied thereto by conventional dye methods. In general, the dyes have improved fastness, for example, to washing, gas (atmospheric fumes) and sublimation.

As described above, the present cationic heterocyclic azo dyes are characterized by a structure which is distinct from other known dyes. This distinctive structure imparts unexpected properties to the present dyes, especially when they are used for dyeing textiles, including improved brightness and fasteness to light. Thus, the dyes of the invention can be expected to be superior to similar but distinct dyes when tested by methods such as described in the A.A.T.C.C. Technical Manual, 1964 edition, depending in part upon the particular dye used and the fiber being dyed.

Textile materials dyed by the cationic heterocyclic azo dyes of the invention are characterized by containing at least about 35% combined acrylonitrile units and up to about 95% acrylonitrile units, and modified, for example, by 85-5% of vinyl pyridine units as described in U.S. Patents 2,990,393 (Re. 25,533) and 3,014,008 (Re. 25,- 539) or modified by 65-5% of vinylpyrrolidone units, for example, as described by U.S. Patent 2,970,783, or modified with 65-5% acrylic ester or acrylamide units as described in U.S. Patents 2,879,253, 2,879,254 and 2,838,- 470. Similar amounts of the other polymeric modifiers mentioned above are also useful. A preferred group of the copolymers readily dyeable with the dyes of the invention are the modacrylic polymers such as described in U.S. Patent 2,831,826 composed of a mixture of (A) 70-95% by weight of a copolymer of from to 65% by weight of vinylidene chloride or vinyl chloride and 70-35% by weight of acrylonitrile, and (B) 305% by weight of a second polymer from the group consisting of (1) homopolymers of acrylamidic monomers of the formula wherein R is selected from the group consisting of hydrogen and methyl, and R and R are selected from the group consisting of hydrogen and alkyl groups of 1-6 carbon atoms, (2) copolymers consisting of at least two of said acrylamidic monomers, and (3) copolymers consisting of at least 50% by weight of at least one of said acrylamidic monomers and not more than 50% by weight of a polymerizable monovinyl pyridine monomer.

A particularly eflicacious group of modacrylic polymers is an acetone soluble mixture of (A) 7095% by weight of a copolymer of 30-65% by weight of vinylidene chloride and 7035% by weight of acylonitrile and (B) 30-5% by weight of an acrylamide homopolymer having the above formula wherein R R and R are as described above. Specific polymers of that group contain 70-95% by weight of (A) a copolymer of from 30-65% by weight of vinylidene chloride and 70-35% by Weight of acrylonitrile and (B) 305% by weight of a lower N-alkylacrylamide polymer such as poly-N-methacrylamide, poly-N- isopropylacrylamide and poly-N-tertiarybutylacrylamide.

The following example illustrates one way in which the cationic heterocyclic azo dyes of the invention can be used to dye acrylonitrile polymer textile material. An amount of 0.1 gram of dye is dissolved by warming in 5 cc. of methyl Cellosolve. A 2% aqueous solution of a non-ionic surfactant, such as Igepal CA (a polymerized ethylene oxide-alkylphenol condensation product), is added slowly until a fine emulsion is obtained and then the dye mixture is brought to a volume of 200 cc. with warm water. Five cc. of a 5% aqueous solution of formic acid or acetic acid are added and then 10 grams of fabric made from an acrylic fiber is entered and, in the case of Orlon 42, the dyeing is carried out at the boil for one hour. In the case of materials made of Verel acrylic fiber the dyebath temperature should not exceed C. in order to avoid damage to the fiber. The dyed material is then washed well with Water and dried.

The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove, and as defined in the appended claims.

13 14 What we claim is: Z is alkylene of up to 6 carbon atoms, phenylene, 1. A compound having the formula methylphenylene, bis(phenylene)methylene, biphenwherein ylylene, dimethylbiphenylylene, bis(methylene)phen- Rl ylene, or naphthylene; and l Y is an anion. I A C 2. A compound accordmg to claim 1 wherein R represents a heterocyclic group having the formula i;

I represents a heterocyclic group having the formula wherein R is lower alkyl; R1 R R is hydrogen or methoxy; and wherein R is hydrogen, methyl, or phenyl;

R is lower alkyl or benzyl; R and R';; each is ethylene; R is hydrogen or methoxy; X and X each 1s --NH; and R is hydrogen, methyl, or phenyl; and Z is phenylene, methylphenylene, bis(methylene)-phen- R is hydrogen or methylthio; ylene, or bis(phenylene)methylene. B and B each is p-phenylene or methyl-p-phenylene; 3. The compound CH3 ('35: H i I (3H3 (1H3 N| \S/LN=N 0 CH3 0 N=Nls lTzoaHloiimv -NH(UJ 0 CIHAN CzHs I CQH;

R and R each is methyl, ethyl, Z-cyanoethyl, phenyl, wherein or tolyl; Y is an anion.

4. The compound r (EH3 H- N N -I u J N=N N=Nl J S S CH3 CH3 0 on? I II ICflLHNi JHN NHJJNHC2HN J R and R;, each is lower alkylene; wherein X and X each is -O- or --NH-; Y is an anion.

5. The compound F $11 3 (IJHU om- L Jami N=NmS "SCHa IYICaHgOCHNCHr- CH2NHCOC2H4N wherein Y is an anion. 8. The compound wherein Y is an anion. 6. The compound Y is an anion.

Y is an anion.

9. The compound 7. The compound US. Cl. X.R. 

